Mixed super critical fluid hydrolysis and alcoholysis of cellulose to form glucose and glucose derivatives

Abstract

The present invention relates to a process for generating glucose and glucose derivatives from the direct contacting of cellulose, hemicelluloses and/or polysaccharides with a mixed super critical fluid system of alcohol and water whereby the partial pressure of the system provides for both alcoholysis and hydrolysis of the material to generate primarily glucose, and glucose derivatives.

We claim: 
     
       1. A method for making an alkyl glucoside or an alkyl pentoside, and optionally making a sorbitol or a polyhydric alcohol, the method comprising:
 (a) (i) combining a feedstock with an alcohol and water,
 wherein the feedstock comprises a cellulosic material, a protein, or both; or 
 
 (ii) combining a feedstock with an alcohol and water, 
 wherein the feedstock comprises a cellulosic material, a hemicellulose material, or both; 
 (b) reacting the feedstock and the alcohol and water at a temperature in the range of between about 140° C. and 350° C., and at a pressure in a range of between about 400 psig and 3500 psig to cleave the cellulosic material to generate a reaction product comprising an alkyl glucoside or an alkyl pentoside, 
 wherein: 
 (i) the feedstock contains at least about 10 wt % cellulosic material based on the dry weight of the feedstock; 
 (ii) the feedstock contains at least about 10 wt % proteins based on the dry weight of the feedstock; 
 (iii) the water content of the combination of (a) before reaction is between about 30 wt % and 300 wt % of the dry weight of the feedstock; or 
 (iv) the alcohol is in an amount from between about 0.5% and 350% wt excess of the hexose or pentose in the feedstock; 
 and 
 (c) separating or isolating the alkyl glucoside or alkyl pentoside from the reaction product of the reaction of (b). 
 
     
     
       2. The method of  claim 1 , wherein the feedstock contains at least about 10 wt % cellulosic material based on the dry weight of the feedstock. 
     
     
       3. The method of  claim 1 , wherein the feedstock contains at least about 10 wt % proteins based on the dry weight of the feedstock. 
     
     
       4. The method of  claim 1 , wherein the water content of the combination of (a) before reaction is between about 30 wt % and 300 wt % of the dry weight of the feedstock. 
     
     
       5. The method according to  claim 1 , wherein said feedstock comprises:
 (a) rice husk, rice bran, corn stover, corn cobs, sugar cane bagasse, palm fiber, palm kernel cake, wood pulp, pine tree material, fir tree material, hardwood tree material, switch grass, microalgae, macro algae or cyanobacteria, or any combination thereof; or 
 (b) a cyanobacteria, a lignocellulose, a cellulose, a polysaccharide, or any combination thereof. 
 
     
     
       6. The method of  claim 1 , wherein the alcohol comprises a methanol, ethanol or propanol, or any combination thereof. 
     
     
       7. The method of  claim 1 , wherein the alcohol is in an amount from between about 0.5% and 350% wt excess of the hexose or pentose in the feedstock. 
     
     
       8. The method of  claim 1 , wherein the hydrogenation catalyst comprises a heterogeneous catalyst or a homogenous catalyst,
 wherein optionally the hydrogenation catalyst comprises a catalyst metal, 
 and optionally the catalyst metal is selected from the group consisting of a platinum, a palladium, a rhodium, a ruthenium, a rainey nickel or a copper chromite. 
 
     
     
       9. The method of  claim 1 , wherein the temperature is in the range of between about 180° C. and 350° C. 
     
     
       10. The method of  claim 1 , wherein the temperature is in the range of between about 240° C. and 350° C. 
     
     
       11. The method of  claim 1 , wherein the pressure is in the range of between about 400 psig and 3500 psig. 
     
     
       12. The method of  claim 1 , wherein the pressure is in the range of between about 1500 psig and 3500 psig. 
     
     
       13. A method for making a hexose, an alkyl glucoside, a pentose, or an alkyl pentoside, and optionally making a sorbitol or a polyhydric alcohol, the method comprising:
 (a) combining a feedstock with an alcohol and water, wherein the feedstock comprises: 
 (i) (1) a polysaccharide, (2) at least 10 wt % cellulosic material based on the dry weight of the feedstock, and (3) at least 10 wt % proteins based on the dry weight of the feedstock; or 
 (ii) (1) a polysaccharide, and (2) at least 10 wt % cellulosic material based on the dry weight of the feedstock; 
 (b) (i) reacting the feedstock and the alcohol and water at a temperature in the range of between about 240° C. to 350° C., and at a pressure in a range of between about 1500 psig to 3500 psig to generate reaction product comprising a hexose and an alkyl glucoside, and/or a pentose and an alkyl pentoside, and if proteins are present the reaction product further comprises amino acids; or 
 (ii) reacting the feedstock and the alcohol and water at a temperature in the range of between about 240° C. and 350° C., and at a pressure in a range of 1500 psig and 3500 psig, to generate a reaction product comprising a hexose and an alkyl glucoside, and/or a pentose and an alkyl pentoside; 
 and 
 (c) separating or isolating the alkyl glucoside or alkyl pentoside from the reaction product of the reaction of (b). 
 
     
     
       14. The method of  claim 13 , wherein the water content of the combination of (a) before reaction is between about 30 wt % and 300 wt % of the dry weight of the feedstock. 
     
     
       15. The method of  claim 13 , wherein the feedstock comprises:
 (a) a cyanobacteria, a lignocellulose, a cellulose, a polysaccharide, or any combination thereof, or 
 (b) a rice husk, a rice bran, a corn stover, a corn cob, a sugar cane bagasse, a palm fiber, a palm kernel cake, a wood pulp, a pine tree material, a fir tree material, a hardwood tree material, a switch grass, a microalgae, a macro algae, a cyanobacteria, or any combination thereof. 
 
     
     
       16. The method of  claim 1 , further comprising hydrolyzing the alkyl glucoside using a weak acid and additional water, wherein the resulting mixture is a glucose and an alcohol. 
     
     
       17. The method of  claim 16 , further comprising removing the alcohol, optionally removing the alcohol by evaporation, centrifuge separation or crystallization. 
     
     
       18. The method of  claim 13 , further comprising hydrolyzing the alkyl glucoside using a weak acid and additional water, wherein the resulting mixture is a glucose and an alcohol. 
     
     
       19. The method of  claim 18 , further comprising removing the alcohol, optionally removing the alcohol by evaporation, centrifuge separation or crystallization. 
     
     
       20. The method of  claim 13 , wherein the hydrogenation catalyst comprises a heterogeneous catalyst or a homogenous catalyst. 
     
     
       21. The method of  claim 20 , wherein the hydrogenation catalyst comprises a catalyst metal, and optionally the catalyst metal is selected from the group consisting of a platinum, a palladium, a rhodium, a ruthenium, a rainey nickel or a copper chromite. 
     
     
       22. The method of  claim 1 , wherein the reaction product is in the form of a reaction product slurry having an insoluble solids portion and a liquid fraction,
 and the reaction product slurry optionally comprises any unreacted feedstock, glucose, alkyl glucosides, sorbitol, excess alcohol, water, lignin, organic salts, inorganic salts. 
 
     
     
       23. The method of  claim 1 , further comprising separating or isolating the alkyl glucoside or alkyl pentoside by a method comprising:
 transferring the reaction product slurry to a Liquid/Solid Separation system to separate the liquid water phase fraction from the insoluble solids portion, including any lignin if contained in the feed, wherein glucose and alkyl glucosides remain with the liquid water phase fraction, 
 and optionally the separated alkyl glucoside is hydrolyzed using weak acid and additional water, and the resulting mixture comprises glucose and alcohol, and optionally the alcohol is removed by evaporation, centrifuge separation, crystallization or a combination thereof, 
 and optionally separating the liquid water phase fraction from the insoluble solids portion comprises use of filtration, carbon treatment, centrifugation or a combination thereof, 
 and optionally the insoluble solids portion is washed with alcohol, water or hydrophobic solvent and sent to storage for re-processing or discharge. 
 
     
     
       24. The method of  claim 1 , further comprising a method for making a sorbitol or a polyhydric alcohol by further reacting the reaction product of step (b) by addition of:
 (i) a hydrogen and a hydrogenation catalyst, or 
 (ii) a hydrogenation catalyst; 
 wherein the presence of the hydrogen and the hydrogenation catalyst, or the hydrogenation catalyst, in the reaction mixture generates a sorbitol or a polyhydric alcohol and a sugar derivative, 
 and optionally the amount of hydrogen ranges from between 1:1 mole wt of the glucose in the feedstock to 1000:1 mole wt of the contained glucose in the feedstock. 
 
     
     
       25. The method of  claim 13 , wherein the reaction product is in the form of a reaction product slurry having an insoluble solids portion and a liquid fraction,
 and the reaction product slurry optionally comprises any unreacted feedstock, glucose, alkyl glucosides, sorbitol, excess alcohol, water, lignin, organic salts, inorganic salts. 
 
     
     
       26. The method of  claim 13 , wherein separating or isolating the alkyl glucoside or alkyl pentoside comprises:
 transferring the reaction product slurry to a Liquid/Solid Separation system to separate the liquid water phase fraction from the insoluble solids portion, including any lignin if contained in the feed, wherein glucose and alkyl glucosides remain with the liquid water phase fraction, 
 and optionally the separated alkyl glucoside is hydrolyzed using weak acid and additional water, and the resulting mixture comprises glucose and alcohol, and optionally the alcohol is removed by evaporation, centrifuge separation, crystallization or a combination thereof, 
 and optionally separating the liquid water phase fraction from the insoluble solids portion comprises use of filtration, carbon treatment, centrifugation or a combination thereof, 
 and optionally the insoluble solids portion is washed with alcohol, water or hydrophobic solvent and sent to storage for re-processing or discharge. 
 
     
     
       27. The method of  claim 13 , further comprising a method for making a sorbitol or a polyhydric alcohol by further reacting the reaction product of step (b) by addition of:
 (i) a hydrogen and a hydrogenation catalyst, or 
 (ii) a hydrogenation catalyst; 
 wherein the presence of the hydrogen and the hydrogenation catalyst, or the hydrogenation catalyst, in the reaction mixture generates a sorbitol or a polyhydric alcohol and a sugar derivative, 
 and optionally the amount of hydrogen ranges from between 1:1 mole wt of the glucose in the feedstock to 1000:1 mole wt of the contained glucose in the feedstock.